Metallic selenide fungicides for outdoor cellulosic textiles



drying the impregnated fabric.

- Ni, Ag, Sn, and Zn.

7 tion:

METALLIC SELENIDE FUNGICIDES FOR OUT- DOOR CELLULOSIC TEXTILES Ralph J.Brysson, New Orleans, and Wilson A. Reeves, Metairie, La., assignors toUnited States of America as represented by the Secretary of AgricultureNo Drawing. Filed May 5, 1960, Ser. No. 27,230

v 1 Claim. (Cl. 117-1385) (Granted under Title 35, US. Code (1952), see.266) A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for. suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to the treatment of textile materials. Moreparticularly, the invention relates to the treatment of textile fabrics,composed mainly of cellu-' resistant to attack by microorganisms whenexposed to direct or indirect sunlight.

It has been found that the objects of the present invention can beachieved by treatment of the cellulosie fabric with selenide saltseither by precipitation in situ alone or precipitation in situ followedby treatment with a suitable binding resin or by impregnation of thecellulosic fabric with an emulsion or solution of the selenide saltsdispersed in a suitable binder. Suitable binders include alkyd resins,urea resins, melamine resins, vinyl resins, styrene resins,cournarone-indene resins, petroleum resins, silicone resins, maleicresins, phenolic resins, polyethylene dispersions, and butadienestyrenecopolymers.

In general, the process of the invention forrendering a cellulosictextile fabric resistant to the attack of micro organism involvesimpregnating the fabric with an aqueous-solvent emulsion systemcontaining an alkyd resin binder and a water insoluble metal selenideand In this aqueous-solvent emulsion system the selenide is present inan amount "nited States Patent 2,977,250 Patented Mar. 28, 1961 ice duckand allowed to air dry. The ratio of the cadmium selenide containingmaterial to the solid resin was approximately 1 to 2. Approximately 2 /2cadmium selenide material and 5% alkyd resin were added to the cottonfabric. Therefore, the fabric actually contained only about .07-5%selenium. This treated duck was were applied to the duck at five levelssufiicient to insure the deposition of at least 0.01% by 7 weight ofselenium on the dried fabric.

Selenide' salts suitable for use in this invention are insolublematerials that contain a non-alkali metal selenide, when the metal isBi, Cd, Co, Cu, Pb, Mn, Hg, These compounds are effective singly, incombination, in combination with selenium, or in combination withselenium and each other. They may be in combination with other materialssuch as heavy non-alkali metal sulfides to produce various colored.rnicroorganism resistant treated .cellulosic textiles.

They may be used in combination with" other conventional textiletreating materials. such as wetting agents,

softeners, stiffness, and others. v

Preparation of these materials can be carried out by any suitable means.

The following nxinv rrn i placed on open backed wooden weather exposureracks in an unshaded essentially suburban area in New Orleans,Louisiana. These racks faced south at an angle of 45 and were soconstructed that all samples were at a minimum of 30 inches above theground. After two years of continuous exposure the sample treated withthe cadmium selenide containing material was free from any detectablemildew or other microorganism staining or attack. A sample of scouredduck and a sample of scoured duck treated with 5% of the alkyd resin(without the cadmium selenide containing material) was badly stainedafter only six months of exposure.

EXAMPLE 2 A dispersion of a finely divided cadmium selenide materialcontaining 23% selenium in an emulsifiable alkyd min binder was appliedto 10.10 oz. cotton duck in the same manner and proportions and exposedas described in Example 1. This cadmium selenide treated cotton duckcontained about 0.69% selenium and showed no visible evidence of mildewor algae staining or attack after 18 months of outdoor exposure andretained 60% of the original fabric strength as compared to an untreatedcontrol sample which was badly discolored by mildew and algae and whichretained only 26% of its original strength when exposed for the sameperiod of time.

EXAMPLE 3 Five pigments containing known amounts of cadmium selenide andcadmium sulfide have been used to treat cotton duck to prevent mildewand algae growth. One sample of pure cadmium selenide and one sample ofcadmium sulfide were also used to treat samples of the duck. Each of theseven cadmium containing materials 'ing from 1% down to .06%. Since oneof the pigments contained 3% by weight of selenide ion, the fabricactually contained only 0.0018% selenium. All of the compounds wereapplied to the fabric samples by first dispersing them in an alkyd resinbinder then padding the fabric, through the emulsion and drying- In eachcase the dry add-on of the alkyd binder was about'3.3%. The alkyd resinused here was the same as that used in Examples 1 and 2. One sample offabric was treated With-the alkyd binder alone as a control fabric.

A description of the compounds and the amount applied to the thirty-fivesamples of cotton fabric is examples, are illustrative of the invengivenin Table I.

7 Table I CONCENTRATION .OF INHIBITORS APPLIED TO FABRIC Selenium Amountof pigment'or Com- Cadmium Containing in pound Applied to Fabric,

Material Material, Percent by Wt.

Percent Pigment1.'. a 1 .5 .25 '.13 i .05 Plgment2 9 1 .5 .25 .13 .06Pigment 3.. 12 1 .5 .25 .13 .06 Pigment 4.. 23 1 .5 .25 .13 .06 Pigment5.. 28 1 .5 .25 .13 .06 Pure CdSe- 41 1 .5 .25 -13 .06 Pure OdS-.--.--.None 1 .5 .25 .13 .06

'The samples were exposed outdoors for eight months inthe mannerdescribed in Example 1. Results' of milgrowth on the fabrics afterexposure are shown in Table II.

of add-on rang- 3 Table 11 Percent Percent Cd+Se Containing Se inMaterial on Fabric Material Applied Gd-l-Sc Containing Msterial Appliedto Fabric mooo a -aki Pigment 1 Pigment 2 Pigment 3 Pure CdS .I

1 =c0mpletely free cl mildew and algae; T=traoe of mildew or algae;X=visible mildew or algae present.

The sample treated with the resin alone showed visible evidence ofmildew and algae growth after two months and the amount continued toincrease for the entire eight month period.

EXAMPLE 4 The selenide containing material can be dispersed with othermaterials to produce desired colors and shades on 25 2.9 gms. of pigmentcontaining CdSe (28% Se) 4.2 gms. chrome yellow pigment 1.5 gms. rawumber pigment .6 gm. lampblack 30.4 gm's. emulsifiable "alkyd resinsolution (50% resin solids).

The above was dispersed by means of a sample size paint mill andemulsified in the following mixture:

208 gms. water 104 gms. toluene 104 gms. mineral spirits This mixturewas applied by padding to 10.10 ounce cotton duck so as to depositapproximately of the cadmium selenide containing material on the cottonfabric. A sample so treated was exposed as described in Example 1 foreight months. The exposed sample was free from all visible signs ofmildew and algae attack or staining. An untreated sample simultaneouslyexposed showed considerable evidence of attack by microorganisms.

We claim:

A process for rendering a cellulosic textile fabric resistant to theattack of microorganisms which coniprises impregnating the cellulosictextile fabric with an aqueous-solvent emulsion system containing analkyd resin binder and a water insoluble metal selenide, and drying theimpregnated fabric, said selenide being present in said aqueous-solventemulsion system in an amount sufficient to insure the deposition of atleast 0.01% by weight of selenium on the dried fabric.

References Cited in the file of this patent UNITED STATES PATENTS

